Metal or metal compound pattern and forming method of pattern, and electron emitting device, electron source, and image-forming apparatus using the pattern

ABSTRACT

The present invention is to provide a method for forming various patterns such as a metal or metal compound pattern, in which the amounts of the materials constituting the pattern which are removed during the formation step can be suppressed to the minimum. The method comprises a resin pattern forming step of forming on the surface of a substrate a resin pattern capable of absorbing a solution containing metal components, an absorbing step of dipping the resin pattern in the solution containing metal components to make the resin pattern absorb the solution containing metal components, a washing step of washing the substrate having formed thereon the resin pattern that has absorbed the solution containing metal components, and a burning step of burning the resin pattern after washing.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The present invention relates to a method for forming a metal ormetal compound pattern by using a solution containing metal components,and a method for manufacturing an electron emitting device, an electronsource and an image-forming apparatus using the pattern. The presentinvention also relates to a metal or metal compound pattern using adesired porosity; and an electron emitting device, an electron sourceand an image-forming apparatus using the pattern.

[0003] 2. Related Background Art

[0004] With respect to a method for forming an electrically conductivepattern used as an electrode, a wiring and the like, conventionallyknown are the following methods: (1) a method of adhering a metal by asputtering method (by a sputtering), patterning a resist and performingetching by an ion-milling method to peel a resist; (2) a method ofprinting an electrically conductive paste to a desired pattern using ascreen printing, and then drying/baking it to form a desiredelectrically conductive pattern; (3) a method of forming an electricallyconductive pattern by transfer; (4) a method of coating an electricallyconductive paste over the entire surface of a substrate, drying/bakingit to form a metal film, covering a desired part of the metal film witha mask such as photo resist and etching the parts other than the desiredparts to form a desired electrically conductive pattern; (5) a method ofimparting the photosensitivity to a metal paste, exposing a desired partthereof and then developing it to form an electrically conductivepattern (Japanese Patent Application Laid-open No. 5-114504); and (6) amethod of allowing a layer formed of gelatin or the like to absorbdroplets having electroconductivity and burning-removing the gelatinlayer to form an electroconductive film (Japanese Patent ApplicationLaid-open No. 9-213211).

[0005] However, the method (4) and the method (5) have a problem inthat, particularly in a case of constituting an electrically conductivepattern by a noble metal such as platinum, a large amount of noble metalcomponents are removed at the time of etching and development, whichresults in much labor and a heavy burden in terms of equipment requiredfor recovering and reusing the components removed. Also, there arisesthe above-described problem not only in the formation of an electricallyconductive pattern but also in the formation of a metal compound patternincluding insulating materials. Accordingly, a solution for this problemhas been demanded.

[0006] With respect to the quality of the formed pattern, the filmpattern formed according to the method (1) has high film density andelectrode properties of the pattern itself have no problem. However, ithas a problem that in the presence of dissimilar metals, the propertiesthereof change with the passage of time because dissimilar metals easilydiffuse and move. Further, in the electron emitting device, thediffusion of dissimilar metals may adversely affect the electronemitting property, which is regarded as a problem (Japanese PatentApplication Laid-open No. 2000-243327). Further, the film patternsformed according to the methods (2) to (5) have low film densities andit is difficult to stably control the film quality. Therefore, forexample, when a plurality of patterns are formed on a substrate, therearises a problem that uneven distribution takes place with respect tothe electrical properties.

[0007] In particular, according to the method (2), it was difficult toform a fine pattern. According to the method (3), it was difficult toform a pattern having a uniform film quality or to form a pattern havingreproducibility.

SUMMARY OF THE INVENTION

[0008] The present invention has been made by taking account of theseproblems inherent in conventional techniques and the object of thepresent invention is to provide a method for forming various patternssuch as a metal or metal compound pattern, in which the amounts of thematerials constituting the pattern which are removed during theformation step can be suppressed to the minimum, and in particular, evenwhen a pattern is constituted by a noble metal such as platinum, thematerials constituting the pattern which are removed during theformation step can be recovered and reused at the minimum load.

[0009] Another object of the present invention is to provide a metal ormetal compound pattern, in particular, preferably an electrode pattern,in which the stability of properties as a metal or metal compoundpattern are maintained and at the same time, the diffusion and movementof dissimilar metals in the presence of dissimilar metals is suppressed.

[0010] According to the present invention, there is provided a method ofmanufacturing a metal or metal compound pattern, the method comprising:a resin pattern forming step of forming on the surface of a substrate aresin pattern capable of absorbing a solution containing metalcomponents; an absorbing step of dipping the resin pattern in thesolution containing metal components to make the resin pattern absorbthe solution containing metal components; a washing step of washing thesubstrate having formed thereon the resin pattern that has absorbed thesolution containing metal components; and a burning step of burning theresin pattern after washing.

[0011] Further, according to the present invention, there is provided amethod of manufacturing a metal or metal compound pattern, the methodcomprising: a resin pattern forming step of forming on the surface of asubstrate a resin pattern capable of absorbing a solution containingmetal components; an absorbing step of coating the solution containingmetal components onto the resin pattern by a spray method or a spin coatmethod to make the resin pattern absorb the solution containing metalcomponents; a washing step of washing the substrate having formedthereon the resin pattern that has absorbed the solution containingmetal components; and a burning step of burning the resin pattern afterwashing.

[0012] Still further, according to the present invention, there isprovided a method of manufacturing a metal or metal compound, the methodcomprising: a resin pattern forming step of forming on the surface of asubstrate a resin pattern capable of absorbing a solution containingmetal components and capable of ion-exchanging the metal components; anabsorbing step of making the resin pattern absorb the solutioncontaining metal components; and a burning step of burning the resinpattern that has absorbed the solution containing metal components.

[0013] Further, according to another aspect of the present invention,there is provided a pattern comprising: a first region having a firstmetal or a first metal compound and having a porosity of 60% or less;and a second region disposed so as to be in contact with the firstregion and having a second metal or a second metal compound which isdifferent from the first metal or the first metal compound.

BRIEF DESCRIPTION OF THE DRAWINGS

[0014]FIG. 1 is a schematic view of the device electrode pattern formedin Example 3 and Example 15; and

[0015]FIG. 2 is a schematic view showing a display panel portion of theimage-forming apparatus manufactured in Example 3 and Example 15.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] The present invention provides a method of forming a pattern inwhich a resin patterned on a substrate is absorbed by dipping it in asolution containing metal components or by coating thereon a solutioncontaining metal components, and then the substrate is washed to formthereon a pattern through a burning step. The present invention alsoprovides a method of forming a pattern in which the above-mentionedsolution containing the metal components is absorbed in a resin patterncapable of absorbing a solution containing metal compounds and capableof ion-exchanging the metal components, and then burning the resinpattern. In particular, the present invention provides a method offorming a metal or metal compound pattern by using a photosensitiveresin and a solution containing metal components. Representativeexamples of the metal or metal compound pattern formed according to thepresent invention include an electrode, a wiring and an insulating layercomposed of a metal oxide. Of the metal or metal compound patternsformed according to the present invention, the forming method of anelectrically conductive pattern is useful, for example, for amanufacturing method of an electron emitting device having an electrode,for a manufacturing method of an electron source having a plurality ofthis electron emitting devices, and particularly for alleviating theburden of recovering and reusing the constituent materials in amanufacturing method of an image-forming apparatus using this electronsource.

[0017] According to another aspect of the present invention, there isprovided a pattern comprising: a first region having a first metal orthe first metal compound and having a porosity of 60% or less; and asecond region disposed so as to come into contact with the first regionand having a second metal or a second metal compound which is differentfrom the first metal or the first metal compound.

[0018] By virtue of the above arrangement, in the first region and thesecond region, for example, used as a device electrode constituting anelectron emitting device, the constitution materials of a wiringconnecting with the above-described device electrode is prevented fromdiffusing and an electron emitting device having preferable propertiescan be provided.

[0019] In the present invention, the term metal means a metal includingeven an alloy. The above description that “The first metal or the firstmetal compound is different from the second metal or the second metalcompound” also refers to a case where these are composed of the sameelement but the ratio thereof is different.

[0020] For example, when each of the first region and the second regionis constituted by a solder as an alloy of tin (Sn) and lead (Pb) at theratio of Sn:Pb=7:3, and Sn:Pb=6:4, respectively, then the first regionand the second region are different from each other and these are withinthe scope of the present invention. Also, when the first region and thesecond region are constituted using a mixed paste of silver (Ag) andlead oxide (PbO) used for a wiring, while varying the mixed ratiothereof between the first and second regions, the first region and thesecond region are different from each other.

[0021] As described above, the present invention may be applied to anelectron emitting device and an image-forming apparatus using thedevice. Examples of the electron emitting device include a surfaceconductive-type electron emitting device in which an electricallyconductive thin film is formed to connect with a pair of deviceelectrodes that are formed so as to oppose with each other on anelectrically insulating substrate, and then this electrically conductivethin film is subjected to a welding treatment referred to as a formingto locally destroy, deform or alter the electrically conductive thinfilm to thereby form a part having electrically high resistanceincluding a crack, and which uses a phenomena that after forming thepart having electrically high resistance including a crack, if a voltageis applied between the device electrodes and a parallel electric currentis applied onto the surface of the electrically conductive thin film, anelectron emission occurs through the part having electrically highresistance including the crack (electron emitting part). Other examplesthereof include an electric field emitting-type electron emitting devicereferred to as “FE-type” or an electron emitting device having ametal/insulating layer/metal-type structure referred to as “MIM-type”.

[0022] Examples of an electron source provided with a plurality ofelectron emitting devices and a wiring for driving a plurality of theelectron emitting devices include an electron source having electronemitting devices disposed in a ladder-like fashion, in which a pluralityof electron emitting devices having a pair of device electrodes aredisposed in a matrix form in an X direction and a Y direction, onedevice electrode and another device electrode of a plurality of theelectron emitting devices, which are disposed in the same line, areconnected to a common wiring and in which, at the same time, an electronfrom the electron emitting devices can be control-driven by an controlelectrode (also referred to as “a grid”) disposed above the electronemitting devices in the orthogonal direction to this wiring.

[0023] Another example of the electron source include an electron sourcein which a plurality of the electron emitting devices are disposed in amatrix form in an X direction and a Y direction, and one deviceelectrode of a plurality of the electron emitting devices that aredisposed in the same line is connected to a common wiring in the Xdirection and another device electrode of a plurality of the electronemitting devices disposed in the same line is connected to a commonwiring in the Y direction. This is a so-called simple matrixarrangement.

[0024] Examples of an image-forming apparatus include those manufacturedby combining the electron source as described above with image-formingmembers forming an image by the irradiation of an electron beam emittedfrom an electron emitting device of this electron source. If animage-forming member having a fluorescent material emitting a visibleradiation by an electron is used, a display panel that may be used as atelevision or computer display can be fabricated. If a photosensitivedrum is used as an image-forming member and a latent image is formed onthis photoreceptor drum by the irradiation of an electron beam can bedeveloped using toner, a copy machine or a printer can be manufactured.

[0025] With respect to the preferred embodiments of the presentinvention, materials used (a solution containing a resin and metalcomponents), the method of forming the metal or metal compound pattern,in particular, the electrically conductive pattern of the presentinvention, a calculation method of the porosity, and the manufacturingmethod of the electron emitting device, the electron source, and theimage-forming apparatus of the present invention are described insequence below.

[0026] (1) Photosensitive Resin

[0027] The resin for use in the present invention is preferably aphotosensitive resin and is not particularly limited as long as theresin pattern formed using the photosensitive resin can absorb asolution containing metal components that is described later. Both awater-soluble photosensitive resin and a solvent-soluble photosensitiveresin may be used. The term “A water-soluble photosensitive resin”refers to a photosensitive resin that allows a development in thedevelopment step described later to be performed with water or adeveloper containing at least 50% by weight of water. The term “Asolvent-soluble photosensitive resin” refers to a photosensitive resinthat allows a development in a development step to be performed with anorganic solvent or a developer containing at least 50% by weight of anorganic solvent.

[0028] The photosensitive resin may be a resin having a photosensitivegroup in the resin structure or may be a resin having mixed therein aphotosensitive agent such as cyclized rubber-bisazide resist. In eitherphotosensitive resin component, a photoreaction initiator or aphotoreaction inhibitor may be mixed as appropriate. The photosensitiveresin may be a type (a negative type) that a photosensitive resincoating soluble in a developing solution turns to be insoluble in adeveloping solution by the photoirradiation or may be of a type (apositive type) in which a photosensitive resin coating insoluble in adeveloping solution turns to be soluble in a developing solution by thephotoirradiation.

[0029] In the present invention, a general photosensitive resin can beused in a wide range as described above. Particularly preferred is anion-exchangeable resin reacting with metal components in a solutioncontaining metal components that is described later. A water-solublephotosensitive resin is also preferably used because a preferable workenvironment can be easily maintained and the resulting waste scarcelyputs a load on nature.

[0030] The water-soluble photosensitive resin will be further described.This water-soluble photosensitive resin may be a resin which uses adeveloper containing at least 50% by weight of water and having addedthereto a lower alcohol such as methyl alcohol or ethyl alcohol forincreasing the drying rate or a component for attaining the dissolutionacceleration or the stability improvement of the photosensitive resincomponents, within the range of less than 50% by weight. From thestandpoint of reducing the environmental load, however, preferred is aresin that allows a development with a developer having a water contentof 70% by weight or more, more preferred is a resin that allows adevelopment with a developer having a water content of 90% by weight ormore and most preferred is a resin that allows a development using onlywater as a developer. Examples of this water-soluble photosensitiveresin include a resin comprising a water-soluble resin such as polyvinylalcohol resin or polyvinyl pyrrolidone resin.

[0031] (2) Solution Containing Metal Components

[0032] The solution for use in the present invention is preferably asolution containing metal components. In this case, the solution may bean organic solvent-type solution comprising an organic solvent-typesolvent containing 50% by weight or more of an organic solvent or may bean aqueous solution comprising an aqueous solvent containing 50% byweight or more of water, as long as it can form a metal or metalcompound film by burning. For such a solution containing metalcomponents, for example, there can be used a solution obtained bydissolving as metal components an organic solvent-soluble or awater-soluble metal organic compound formed of platinum, silver,palladium or copper in an organic solvent-type solvent or an aqueoussolvent. Among these, a solution in which a platinum organic compound isdissolved is preferably used because an electrically conductive patternwhich is very chemically stable can be easily obtained.

[0033] Similarly to the above-described photosensitive resin, thesolution containing metal components for use in the present invention ispreferably an aqueous solution because a preferable work environment canbe easily maintained and the resulting waste scarcely puts a load onnature. The aqueous solvent for this aqueous solution may be an aqueoussolvent containing 50% by weight or more of water and having addedthereto, for example, a lower alcohol such as methyl alcohol or ethylalcohol for accelerating the drying rate or having added thereto acomponent for achieving the dissolution acceleration or the stabilityimprovement of the above-described metal organic compound, within therange of less than 50% by weight. From the standpoint of reducing theenvironmental load, however, the water content of the solvent ispreferably 70% by weight or more, more preferably 90% by weight or more,and most preferably, the solvent is all water.

[0034] Examples of a water-soluble metal organic compound which can forman electrically conductive film particularly by burning include acomplex compound of gold, platinum, silver, palladium, copper or thelike.

[0035] The complex compound is preferably the one such that the ligandthereof is constituted by a nitrogen-containing compound having at leastone hydroxyl group in a molecule. Among the complex compounds in whichthe ligand thereof is constituted by a nitrogen-containing compoundhaving at least one hydroxyl group in a molecule, preferred is, forexample, a complex compound such as alcoholamine, (ethanolamine,propanolamine, isopropanolamine and butanolamine or the like), selinenoland TRIS, in which the ligand thereof is constituted by any one ofnitrogen-containing compounds having 8 or less carbon atoms or by two ormore thereof.

[0036] The reasons why the complex compound is preferably used includeits high water-solubility and low crystallinity. For example, in acommercially available ammine complex, a crystal precipitates during thedrying and an uniform film is hardly obtained in some cases. If a“flexible” ligand such as those constituted by aliphatic alkylamine isused, the crystallinity can be lowered but the water-solubility maydecrease due to hydrophobic property of an alkyl group. On the otherhand, if a complex compound wherein the ligand is constituted asdescribed above is used, a high water-solubility and a low-crystallinitymay be obtained at the same time.

[0037] For the purpose of improving the film quality of the electricallyconductive pattern obtained and improving the adhesion of theelectrically conductive pattern to a substrate, for example, an elementform such as rhodium, bismuth, ruthenium, vanadium, chromium, tin, leadand silicon or a compound thereof is preferably contained as a componentof the above-described metal compound.

[0038] (3) Method of Forming Electrically Conductive Pattern

[0039] The formation of the electrically conductive pattern according tothe present invention can be performed through the resin pattern formingsteps as described below (coating step, drying step, exposing step anddeveloping step), absorbing step, washing step, burning step, ifdesired, milling step.

[0040] The coating step is a step for coating the above-describedphotosensitive resin on an insulating substrate on which an electricallyconductive pattern is to be formed. This coating can be performed usingvarious printing methods (screen printing, off-set printing,flexographic printing), spinner method, dipping method, spray method,stamp method, rolling method, slit coater method, ink jet method or thelike.

[0041] The drying step is a step for vaporizing a solvent in aphotosensitive resin film that has been coated on the substrate in theabove-described coating step to thereby dry the coating. The coatingfilm can be dried at a room temperature but preferably dried throughheating for shortening the drying time. The drying by heating can beperformed using, for example, a no-wind oven, a dryer or a hot plate andcan be generally performed by placing the film under a temperature of 50to 100° C. for 1 to 30 minutes, though the conditions vary depending onthe formulation or coating amount of the composition coated for formingan electrode and a wiring.

[0042] The exposing step is a step for exposing the photosensitive resinfilm on the substrate, which was dried in the above-described dryingstep, according to the predetermined resin pattern (for example, apredetermined shape of an electrode or a wiring). The region to beexposed by the photoirradiation in the exposing step varies depending onwhether the photosensitive resin used is a negative-type resin or apositive-type resin. In the case of a negative-type resin that becomesinsoluble in a developing solution by the photoirradiation, an exposureis performed by irradiating light to the region to be left as a desiredresin pattern. On the other hand, in the case of a positive-type resinthat becomes soluble in a developing solution by the photoirradiation,contrary to a negative-type resin, an exposure is performed byirradiating light to the region other than the region to be left as aresin pattern. The photoirradiation region and the non-irradiationregion can be selected in the same manner as performed in a general maskformation by photoresist.

[0043] The developing step is a step for removing the photosensitiveresin film in the region other than the region to be left as a desiredresin pattern, in the photosensitive resin film that was exposed in theabove-described exposing step. When the photosensitive resin is anegative type resin, a photosensitive resin film in the region where thephotoirradiation was not performed is soluble in a developing solutionand a photosensitive resin film in the region exposed byphotoirradiation is made insoluble in a developing solution. Therefore,a development can be performed by dissolving and removing with adeveloping solution a photosensitive resin film in a non-photoirradiatedportion that has not become insoluble in a developing solution. When thephotosensitive resin is a positive-type resin, a portion of thephotosensitive resin film which is not photoirradiated is insoluble in adeveloping solution and a portion of the photosensitive resin film thatis exposed by the photoirradiation becomes soluble in a developingsolution. Therefore, a development can be performed by dissolving andremoving with a developing solution a photosensitive resin film in aphotoirradiated portion which became soluble in a developing solution.

[0044] In the case of using a water-soluble photosensitive resin, adeveloping solution used is, for example, water or the same developingsolution as used in a general water-soluble photoresist. In the case ofusing an organic solvent resin, a developing solution used may be anorganic solvent or the same developing solution as used in asolvent-type photoresist. Here, as a step for forming a resin pattern, aforming step using a photosensitive resin has been described. In thecase of using a resin other than the photosensitive resin, a resinpattern may be formed by lift-off or the like.

[0045] The absorbing step is a step for making the resin pattern formedas described above absorb the above-described solution containing metalcomponents. The absorption can be performed by bringing the formed resinpattern into contact with the solution containing metal components. Morespecifically, the absorption can be performed, for example, by a dippingmethod in which the formed resin pattern is dipped in the solutioncontaining metal components or a coating method in which the solutioncontaining metal components is coated onto the formed resin pattern by amethod such as spray method or spin-coating method. Before contactingthe resin pattern with the solution containing metal components, forexample, in the case of using the above-described aqueous solution, theresin pattern may be swelled in advance using the above-describedaqueous solvent.

[0046] The washing step is a step performed after making the resinpattern absorb the solution containing metal components, for removingand washing an excess solution adhering to the resin pattern or anexcess solution adhering to the parts other than the resin pattern. Thiswashing step can be performed using the same washing solution as thesolvent in the solution containing metal components, by a method ofdipping in this washing solution a substrate having formed thereon theresin pattern or by a method of spraying the washing solution onto asubstrate having formed thereon the resin pattern. The washing performedhere is not limited to a washing with a washing solution as long as theexcess solution can be washed away and thus it can be performed, forexample, by a method using air spraying or vibration. In this washingstep, the solution containing metal components may be slightly removed.However, the amount removed is extremely small and therefore, even ifthis is recovered and reused, can be drastically reduced as comparedwith the conventional method.

[0047] The burning step is a step for burning a resin pattern (aphotosensitive resin film in a photoirradiation portion in the case of anegative-type resin and a photosensitive resin film in anon-photoirradiation portion in the case of a positive-type resin) thatwas obtained through the developing step, the absorbing step and thewashing step, and decomposing and removing the organic components in theresin pattern to form an electrically conductive film using the metalcomponents in the solution containing metal components absorbed in theresin pattern. The burning can be performed in an atmosphere when theelectrically conductive film to be formed is a noble metal film. Also,the burning can be performed in a vacuum or a deoxidation atmosphere(for example, in an inert gas atmosphere such as nitrogen) when theelectrically conductive film to be formed is a film formed of a metalthat easily oxidize, such as copper and palladium. In the case offorming an insulating pattern, an insulant can be formed by burning Pbor the like in an oxygen atmosphere (such as in an air). The burning canbe generally performed by placing the resin pattern under a temperatureof 400 to 600° C. for several minutes to several tens of minutes, thoughthe conditions vary according to the kinds of organic componentscontained in the resin pattern. The burning can be performed, forexample, by using a circulating hot air oven. By this burning, anelectrically conductive pattern can be formed on a substrate as a metalfilm having a shape according to the predetermined pattern.

[0048] After the burning step, a milling step may be performed ifneeded. The milling step is a step of patterning a metal film formed ona substrate surface. The ion milling method used may be any of thegenerally used methods. The resist used may be a positive resist or anegative resist. In exposure, the photosensitive resin film is exposedusing a predetermined mask and developed to obtain a predeterminedpattern. The exposed surface is etched by an ion milling method or thelike. The etching can be performed by any method as long as the metalsurface can be etched. Finally, the resist is peeled off, and thepeeling solution may be selected as appropriate according to the kind ofthe resist used.

[0049] The preferable embodiment of the present invention was describedabove. According to this embodiment, a pattern can be formed with a highutilization efficiency of materials and at a low cost.

[0050] When forming a metal or metal compound pattern according to theabove-described preferable embodiment, it is important to control theabsorption ability of a resin pattern such as control of the resinpattern thickness, and to control the absorption conditions in theabsorbing step such as control of the dipping time or the coating time,for controlling the electrical properties of the formed pattern as wellas the function of preventing diffusion of dissimilar metals. By thiscontrol, the porosity of formed pattern can be desirably controlled.

[0051] Incidentally, the method for obtaining a pattern having a desiredporosity is not limited to the above-described manufacturing method, anda pattern having a desired porosity can also be obtained by the methodaccording to Examples 11 and 13 as described later.

[0052] Next, the porosity of the film pattern formed according to thepresent invention will be described in detail below.

[0053] (4) Porosity of Metal or Metal Compound Pattern

[0054] Diffusion Movement of Contamination Component and Stability ofSheet Resistance.

[0055] The film structure of the present invention, in which 60% or lessof porosity (40% or more of density) is provided, will be described.

[0056] Here, the porosity of a metal film pattern in the case of usingit as an electrode will be described. As described above, with regard tothe film quality of a metal film manufactured by sputtering method, theporosity is almost 0% (i.e., the density is 100%) and thus the densityapproaches that of pure metal. By virtue of this, the metal film patternis used as an electrode which is stable in electrode properties. It isfound that when this electrode is joined to dissimilar metals orcontamination metal compounds, these dissimilar metals or contaminationmetal compounds diffuse and move. For example, in a case where Ag of thelike is printed on a Pt electrode by sputtering method, a large amountof Ag diffuses on the Pt electrode. Accordingly, due to the diffusion ofdissimilar metals on the Pt electrode, the electrical properties of theelectrode change, which often becomes a problem.

[0057] It was verified that, when, in particular, Ag or the likediffuses to an electrode constituting an electron emitting device, thediffusion of dissimilar metals exerts great influence on electronemitting properties (Japanese Patent Application Laid-open No.2000-243327). As a result of our studies, it was proved that suchdiffusion of dissimilar metals can be suppressed by providing voids on ametal or metal compound pattern. From the standpoint of preventing thediffusion of dissimilar metals, it is effective that the patternpreferably has the porosity of 10% or more, more preferably 20% or more.In particular, when the diffusion of dissimilar metals such as Ag to anelectron emitting device takes place, the electron emitting propertygreatly changes depending on the diffusion amount, and therefore thediffusion amount of the dissimilar metals must be suppressed to such adegree that does not cause any adverse influence on electron emittingproperty. In order to attain this, it was revealed that the porosity ispreferably 10% or more, and more preferably 20% or more.

[0058] On the other hand, when the porosity is 60% or more (density is40% or less), the film becomes porous. In case of joining such anelectrode with dissimilar metals, contamination metal compounds or thelike, it was found that, since a movement path of the dissimilar metalto be diffused is porous, an environment where it is difficult for thedissimilar metal to move is formed. However, such a porous electrodehaving the porosity of 60% or more is inferior in the resistancestability, and therefore there is a case where the porous electrode maynot obtain stable properties. This also gives rise to a problem not onlyin an electrically conductive pattern such as an electrode but also inan insulating pattern because the electrical properties (insulatingproperty) are insufficient.

[0059] During the formation of an electrode on a large substrate such asPDP, the film thickness distribution may vary on the order of ±20% insuch a porous electrode. In such a case, the variation of the resistancevalue is greater than that of the film thickness distribution, which isa problem as a device using the electrode.

[0060] In view of this, in the metal or metal compound pattern of thepresent invention, the variation of sheet resistance can be minimizedand moreover, there arises no problem in electrode properties. Further,in the case of using the pattern as the electrode of the electronemitting device, the diffusion movement of dissimilar metals orcontamination metal compounds can be suppressed and the degradation ofelectron emitting property can be suppressed.

[0061] Calculation Method of Porosity

[0062] The porosity as described in the present invention is calculatedbased on the measured value of density. First, the calculation method ofdensity is described Pt electrode as an example. The density is providedas the Pt abundance per unit volume.

Pt density=(Pt abundance of the present invention/film thickness)/(Ptabundance of reference/film thickness)

[0063] Where, the Pt abundance of reference is a Pt abundance of Ptpattern formed by a sputtering process. Pt abundance was measured usingEPMA (electron probe•microanalyzer).

[0064] On the basis of the thus obtained density, the porosity isprovided as:

[0065] Pt porosity=1−Pt density. The film thickness was measured using astylus system thicknessmeter.

[0066] (5) Manufacturing Method of Electron Emitting Device, ElectronSource and Image-Forming Apparatus

[0067] The above-described electrically conductive pattern formationmethod of the present invention may be suitably applied to amanufacturing method of: an electron emitting device comprisingelectrodes; an electron source providing a plurality of electronemitting devices having electrodes and a wiring for driving theplurality of electron emitting devices; and further an image-formingapparatus comprising this electron source and an image-forming memberfor forming an image by the irradiation of electron beam emitted from anelectron emitting device of the electron source. More specifically, forthe manufacture of the electron emitting device, an electrode is formedaccording to the method of the present invention; and for themanufacture of the electron source or the image-forming apparatus, oneor both of the electrodes of the electron emitting device and the wiringused is (are) formed according to the method of the present invention,whereby the amount of materials constituting the electrode and/or thewiring which are removed during the manufacturing step can be greatlyreduced and the time and labor required for processing such materialsremoved during the manufacture can be greatly reduced.

[0068] As described hereinabove, preferred examples of the electronemitting device having the electrodes that are manufactured using theelectrically conductive pattern forming method of the present inventionpreferably includes a cold cathode device such as a surfaceconductive-type electron emitting device, a field emission-type(FE-type) electron emitting device and a metal/insulatinglayer/metal-type (MIM-type) electron emitting device. Among these,particularly preferred is a surface conductive-type electron emittingdevice in which a large number of electrodes of electron emittingdevices can be easily formed at one processing using the method of thepresent invention. According to the method of the present invention,simultaneous with formation of the device electrodes for the pluralityof electron emitting devices, a wiring necessary for driving eachelectron emitting device can be formed. Therefore, the electron sourcehaving a plurality of the electron emitting devices can be easilymanufactured and further, the manufacture of an image-forming apparatus,which is achieved by combining this electron source with animage-forming member for forming an image by the irradiation of anelectron beam from the electron emitting device constituting theelectron source, can be made significantly easier.

EXAMPLES

[0069] The present invention is described in greater detail below byreferring to the Examples, however, the present invention is not limitedto these examples.

Example 1

[0070] A solution obtained by adding 0.06 wt % of an amine silanecoupling agent (KBM-603, produced by Shin-Etsu Chemical Co., Ltd.) to aphotosensitive resin (sun resiner BMR-850, produced by Sanyo Kasei Co.,Ltd.) was coated over the entire surface of a glass substrate (75 mm inlength×75 mm in width×2.8 mm in thickness) with a roll coater and driedat 45° C. for 2 minutes using a hot plate. Subsequently, using anegative photomask, the substrate and the mask were brought into contactwith each other, and an exposure was performed thereon for 2 seconds inexposing time by an ultra-high pressure mercury lamp (illuminance: 8.0mW/cm²) as a light source. Thereafter, the resulting substrate wasprocessed by dipping for 30 seconds in pure water as a developer, thusobtaining an objective resin pattern. The film thickness of the resinpattern obtained was 1.55 μm.

[0071] This resin pattern-formed substrate was dipped in pure water for30 seconds and, then, dipped in a Pt—Pb solution (platinum (II)monoethanolamine acetate complex.platinum content: 2% by weight/lead(II) acetate.lead content: 200 ppm) for 60 seconds.

[0072] Subsequently, the substrate was taken out from the Pt—Pbsolution, washed with flowing water for 5 seconds to wash the Pt complexsolution between the resin patterns, dewatered by spraying thereon airand dried for 3 minutes by a hot plate at 80° C.

[0073] Thereafter, the substrate dried was burned at 500° C. for 30minutes in a circulating hot air oven to form a platinum electrodehaving a distance between electrodes of 20 μm, a width of 60 μm, alength of 120 μm and a thickness of 20 nm.

[0074] The sheet resistance of this electrode was 60 Ω/□.

Example 2

[0075] A platinum electrode was formed in the same manner as in Example1 except for using a Pt solution (tetraammineplatinum (II) acetatecomplex.platinum content: 2% by weight) as a metal organic compoundsolution.

[0076] The thickness of this electrode was 25 nm and the sheetresistance thereof was 40 Ω/□.

Example 3

[0077] A platinum electrode was formed in the same manner as in Example1 except for using a Pt—Pb solution (tetraammineplatinum (II) acetatecomplex.platinum content: 2% by weight/lead (II) acetate.lead content:200 ppm) as a metal organic compound solution.

[0078] The thickness of this electrode was 30 nm and the sheetresistance thereof was 55 Ω/□.

Example 4

[0079] Using the electrically conductive pattern forming method of thepresent invention, a plurality of surface conductive-type electronemitting devices were manufactured and, moreover, a wiring for drivingthis plurality of surface conductive-type electron emitting devices wasformed to thereby manufacture an electron source. Further, animage-forming apparatus was manufactured using this electron source. Themanufacturing procedure thereof will be described below on the basis ofFIG. 1 and FIG. 2.

[0080] Step 1: On a glass-made substrate 1 having a size of 300 mm inlength×300 mm in width×2.8 mm in thickness, a plurality of deviceelectrode pairs (first region) as shown in FIG. 1 were manufactured inthe same manner as in Example 1.

[0081] The device electrode pair in this Example was formed by opposinga device electrode A having a width of 60 μm and a length of 480 μm to adevice electrode B having a width of 120 μm and a length of 200 μm in anelectrode gap of 20 μm. The device electrode pairs were disposed on thesubstrate 1 in a matrix form by adjusting so that the pitch between thedevice electrode pair was 300 μm in a lateral direction and 650 μm in alongitudinal direction and the number of device electrode pairs was720×240. A platinum film pattern having a size of 1 cm×1 cm was formedat the same time as the formation of the device electrode pair. Thesheet resistance in that case was measured and it was found to be 26Ω/□.

[0082] Step 2: As shown in FIG. 2, an X direction wiring 2 (secondregion) connecting one device electrode A of the device electrode pairin each line was provided using an Ag paste by a screen printing method.Subsequently, an interlayer insulating layer (not shown in the figure)having a thickness of 20 μm was provided by a screen printing method,and a Y-direction wiring 3 (second region) connecting another deviceelectrode B of the device electrode pair in each line was providedthereon in the same manner as in the X-direction wiring 2 and thesubstrate was burned. In this manner, the X-direction wiring 2 and theY-direction wiring 3 were provided.

[0083] Step 3: The substrate 1 having formed thereon the X-directionwiring 2 and the Y-direction wiring 3 in Step 2 was washed with purewater.

[0084] Step 4: In an aqueous solution having dissolved therein polyvinylalcohol in a concentration of 0.05% by weight, 2-propanol in aconcentration of 15% by weight and ethylene glycol in a concentration of1% by weight, a palladium-monoethanolamine acetate complex was dissolvedso as to have a palladium concentration of about 0.15% by weight,whereby a light yellow aqueous solution was obtained.

[0085] By an ink jet method, droplets of the above-described aqueoussolution were imparted four times to the same portion from the upperposition of the device electrodes A and B constituting each deviceelectrode pair so as to straddle the device electrodes A and B and to begiven within the electrode gap (dot size=about 100 μm).

[0086] The substrate 1 having given thereon the droplets of the aqueoussolution was burned for 30 minutes in a burning oven at 350° C., apalladium thin film 4 for connecting between the device electrodes A andB constituting the device electrode pair was formed between each deviceelectrode pair, and then the substrate 1 was fixed on a rear plate 5.

[0087] Step 5: A face plate 10, in which a fluorescent film 8 and ametal back 9 were formed on the inner surface of a glass-made substrate7 that is different from the substrate 1, was caused to face the rearplate 5, and these were sealed through a supporting frame 6 to therebyconstitute an envelope 11. To the supporting frame 6, an air supply andexhaust pipe used for ventilating and exhausting air was adhered inadvance.

[0088] Step 6: After exhausting the inside of the envelope to 1.3×10⁻⁵Pa through the air supply and exhaust pipe, a forming was performed inevery line in a manner that, by using X-direction terminals D_(x1) toD_(xn) ranging with each X-direction wiring 2 and the Y-directionterminals D_(y1) to D_(ym) ranging with each Y-direction wiring 3, avoltage was applied between the device electrode pairs in each line toproduce a cracking part having a size of tens of μm on the palladiumthin film 4 between the device electrodes A and B, whereby a surfaceconductive-type electron emitting device was formed.

[0089] Step 7: After exhausting the inside of the envelope 11 to1.3×10⁻⁵ Pa, benzonitrile was introduced into the envelope 11 from theair supply and exhaust pipe until the inside of the envelope 11 iselevated to 1.3×10⁻² Pa. In the same manner as in the above-describedforming, a pulse voltage was fed between each device electrode pair andan activation for depositing a carbon on the cracking portion of thepalladium thin film was performed. The pulse voltage was applied for 25minutes to each line.

[0090] Step 8: The inside of the envelope 11 was sufficiently exhaustedthrough the air supply and exhaust pipe and, then, further exhaustedwhile heating the entire envelope 11 at 250° C. for 3 hours. Finally, agetter was flashed thereto and the air supply and exhaust pipe wassealed.

[0091] In this manner, a display panel as shown in FIG. 2 wasmanufactured, and a driving circuit comprising a scan circuit, a controlcircuit, a modulation circuit and a d.c. voltage source (all are notshown) was connected thereto, thereby manufacturing a panel-shapedimage-forming apparatus.

[0092] A predetermined voltage was applied by time sharing to eachsurface conductive-type electron emitting device through the X-directionterminals D_(x1) to D_(xn) and the Y-direction terminals D_(Y1) toD_(Ym), and a high voltage was applied to the metal back 9 through thehigh voltage terminal 12, whereby an arbitrary matrix image pattern canbe displayed with a preferable image quality. Note that, when the panelwas decomposed and the diffusion of Ag to the electron emitting devicewas measured, it was confirmed that the diffusion of Ag was sufficientlyprevented.

[0093] In this Example, the manufacturing method of Example 1 wasapplied to form the device electrode. However, in the constitution inwhich the wiring electrode in contact with other metal, provided thatthe manufacturing method of Example 1 was applied to the formation ofthe wiring, the same effects as the above can be obtained.

Example 5

[0094] An image-forming apparatus was manufactured in the same manner asin Example 4 except for using a Pt—Pb solution (tetraammineplatinum (II)acetate complex platinum content: 2% by weight/lead (II) acetate leadcontent: 200 ppm) as a metal organic compound solution. An arbitrarymatrix image pattern was able to be displayed with a preferable imagequality.

Example 6

[0095] A solution obtained by adding 0.06 wt % of an amine silanecoupling agent (KBM-603, produced by Shin-Etsu Chemical Co., Ltd.) to aphotosensitive resin (sun resiner BMR-850, produced by Sanyo Kasei Co.,Ltd.) was coated over the entire surface of a glass substrate (75 mm inlength×75 mm in width×2.8 mm in thickness) with a spin coater and driedat 45° C. for 2 minutes using a hot plate. Subsequently, using anegative photomask, the substrate and the mask were brought into contactwith each other, and an exposure was performed thereon for 2 seconds inexposing time by an ultra-high pressure mercury lamp (illuminance: 8.0mW/cm²) as a light source Thereafter, the resulting substrate wasprocessed by dipping for 30 seconds in pure water as a developer, thusobtaining an objective pattern. The film thickness of the pattern formedwas 0.98 μm.

[0096] This substrate was dipped in pure water for 30 seconds and, then,dipped in a Pt complex solution (platinum (II) monoethanolamine acetatecomplex.platinum content: 2% by weight) for 30 seconds.

[0097] Subsequently, the substrate was taken out from the Pt complexsolution, washed with a flowing water for 5 seconds to wash the Ptcomplex solution between the patterns, dewatered with air and dried for3 minutes by a hot plate at 80° C.

[0098] Thereafter, the substrate dried was burned at 500° C. for 30minutes in a circulating hot air oven to form a platinum electrodehaving a thickness of 30 nm.

[0099] The sheet resistance of this electrode was 80 Ω/□.

Example 7

[0100] A solution obtained by adding 0.06 wt % of an amine silanecoupling agent (KBM-603, produced by Shin-Etsu Chemical Co., Ltd) to aphotosensitive resin (sun resiner BMR-850, produced by Sanyo Kasei Co.,Ltd.) was coated over the entire surface of a glass substrate (75 mm inlength×75 mm in width×2.8 mm in thickness) with a spin coater and driedat 45° C. for 2 minutes using a hot plate. Subsequently, using anegative photomask, the substrate and the mask were brought into contactwith each other, and an exposure was performed thereon for 2 seconds inthe exposing time by an ultra-high pressure mercury lamp (illuminance:8.0 mW/cm²) as a light source. Thereafter, the resulting substrate wasprocessed by dipping for 30 seconds in pure water as a developer, thusobtaining an objective pattern. The film thickness of the pattern formedwas 1.08 μm.

[0101] This pattern formed-substrate was dipped in pure water for 30seconds and, then, dipped in a Pt—Pb solution (platinum (II)monomethanolamine acetate complex platinum content: 2% by weight/lead(II) acetate lead content: 200 ppm) for 30 seconds.

[0102] Subsequently, the substrate was taken out from the Pt—Pbsolution, washed with flowing water for 5 seconds to wash the Pt—Pbsolution between the patterns, dewatered with air and dried for 3minutes by a hot plate at 80° C.

[0103] Thereafter, the substrate dried was burned at 500° C. for 30minutes in a circulating hot air oven to form a platinum electrodehaving a distance between electrodes of 20 μm, a width of 60 μm, alength of 120 μm and a thickness of 40 nm.

[0104] The sheet resistance of this electrode was 120 Ω/□.

Examples 7-2

[0105] A platinum electrode was formed in the same manner as in Example7 except for changing the metal organic compound solution to a Pt—Rusolution (platinum (II) monoethanolamine acetate complex.platinumcontent: 2% by weight/ruthenium (III) chloride.ruthenium content: 200ppm) and changing the dipping time to 120 seconds. A platinum electrodehaving a distance between electrodes of 20 μm, a width of 60 μm, alength of 120 μm and a thickness of 42 nm was formed. The sheetresistance of this electrode was 12 Ω/□.

Examples 7-3

[0106] A platinum electrode was formed in the same manner as in Example7 except for changing the metal organic compound solution to a Pt—Snsolution (platinum (II) monoethanolamine acetate complex.platinumcontent: 2% by weight/stannum (III) chloride.stannum content: 200 ppm)and changing the dipping time to 30 seconds. A platinum electrode havinga distance between electrodes' of 20 μm, a width of 60 μm, a length of120 μm and a thickness of 56 nm was formed. The sheet resistance of thiselectrode was 80 Ω/□.

Examples 7-4

[0107] A platinum electrode was formed in the same manner as in Example7 except for changing the metal organic compound solution to a Pt—Vsolution (platinum (II) monoethanolamine acetate complex platinumcontent: 2% by weight/vanadyl (IV) salfate vanadium content: 200 ppm)and changing the dipping time to 60 seconds. A platinum electrode havinga distance between electrodes of 20 μm, a width of 60 μm a length of 120μm and a thickness of 38 nm was formed. The sheet resistance of thiselectrode was 64 Ω/□.

Example 8

[0108] A resin (polyvinyl alcohol) was coated over the entire surface ofa glass substrate (75 mm in length×75 mm in width×2.8 mm in thickness)with a spin coater and dried at 45° C. for 2 minutes using a hot plate.Subsequently, the entire surface of the substrate was exposed for 2seconds in exposing time by an ultra-high pressure mercury lamp(illuminance: 8.0 mW/cm²) as a light source. Thereafter, the resultingsubstrate was processed by dipping for 30 seconds in pure water as adeveloper. The film thickness thereof was 1.85 μm.

[0109] This substrate was dipped in pure water for 30 seconds and, then,dipped in a Pt—Pb solution (platinum (II) monoethanolamine acetatecomplex.platinum content: 2% by weight/lead (II) acetate.lead content:200 ppm) for 120 seconds.

[0110] Subsequently, the substrate was taken out from the Pt—Pbsolution, washed with a flowing water for 5 seconds to wash the Pt—Pbsolution between the patterns, dewatered with air and dried for 3minutes by a hot plate at 80° C.

[0111] Thereafter, the substrate dried was burned at 500° C. for 30minutes in a circulating hot air oven to form a platinum electrodehaving a distance between electrodes of 20 pm, a width of 60 μm, alength of 120 μm and a thickness of 60 nm.

[0112] The sheet resistance of this electrode was 160 Ω/□.

[0113] Subsequently, a resist (positive-type resist LC100/10 cp,produced by Shipley Company) was coated (1200 rpm/5 seconds, filmthickness: 1.3 micron) on this substrate with a spinner.

[0114] The coated resist was etched (etching conditions are:acceleration voltage: 500 V, current: 600 mA, deceleration voltage: 200V, gas seed: argon 255 CCM and carrier speed: 5 mm/second) by an ionmilling method, and then the resist was peeled off using a resistpeeling solution (1112A, produced by Shipley Company) to form anobjective pattern and a platinum electrode having a distance betweenelectrodes of 20 μm, a width of 60 μm and a length of 120 μm.

Example 8-2

[0115] A platinum electrode was formed in the same manner as in Example8 except for changing the metal organic compound solution to a Pt—Znsolution (platinum (II) monoethanolamine acetate complex.platinumcontent: 2% by weight/zinc (II) acetate.zinc content: 200 ppm) andchanging the dipping time to 15 seconds.

[0116] A platinum electrode having a distance between electrodes of 20μm, a width of 60 μm, a length of 120 μm and a thickness of 44 nm wasformed. The sheet resistance of this electrode was 250 Ω/□.

Example 8-3

[0117] A platinum electrode was formed in the same manner as in Example8 except for changing the metal organic compound solution to Pt-Rhsolution (platinum (II) monoethanolamine acetate complex.platinumcontent: 2% by weight/rhodium (III) nitrate.rhodium content: 200 ppm)and changing the dipping time to 60 seconds.

[0118] A platinum electrode having a distance between electrodes of 20μm, a width of 60 μm, a length of 120 μm and a thickness of 51 nm wasformed. The sheet resistance of this electrode was 190 Ω/□.

Example 8-4

[0119] A platinum electrode was formed in the same manner as in Example8 except for changing the metal organic compound solution to a Pt—Crsolution (platinum (II) monoethanolamine acetate complex platinumcontent: 2% by weight/chromium (III) acetate.chromium content: 200 ppm)and changing the dipping time to 60 seconds.

[0120] A platinum electrode having a distance between electrodes of 20μm, a width of 60 μm, a length of 120 μm and a thickness of 43 nm wasformed. The sheet resistance of this electrode was 99 Ω/□.

Example 9

[0121] A resin (polyvinyl alcohol) was coated over the entire surface ofa glass substrate (75 mm in length×75 mm in width×2.8 mm in thickness)with a spin coater and dried at 45° C. for 2 minutes using a hot plate.Subsequently, the entire surface of the substrate was exposed for 2seconds in exposing time by an ultra-high pressure mercury lamp(illuminance: 8.0 mW/cm²) as a light source. Thereafter, the resultingsubstrate was processed by dipping for 30 seconds in pure water as adeveloper. The film thickness thereof was 2.3 μm.

[0122] This substrate was dipped in pure water for 30 seconds and, then,dipped in a Pt—Pb solution (platinum (II) monoethanolamine acetatecomplex.platinum content: 2% by weight/lead (II) acetate.lead content:200 ppm) for 60 seconds.

[0123] Subsequently, the substrate was taken out from the Pt—Pbsolution, washed with flowing water for 5 seconds to wash the Pt—Pbsolution between the patterns, dewatered with air and dried for 3minutes by a hot plate at 80° C.

[0124] Thereafter, the substrate dried was burned at 500° C. for 30minutes in a circulating hot air oven to form a platinum electrodehaving a distance between electrodes of 20 μm, a width of 60 μm, alength of 120 μm and a thickness of 60 nm.

[0125] The sheet resistance of this electrode was 39 Ω/□.

[0126] Subsequently, a resist (positive-type resist LC100/10 cp,produced by Shipley Company) was coated (1200 rpm/5 seconds, filmthickness: 1.3 micron) on this substrate with a spinner.

[0127] The coated resist was etched (etching conditions are:acceleration voltage: 500 V, current: 600 mA, deceleration voltage: 200V, gas seed: argon 255 CCM and carrier speed: 5 mm/second) by an ionmilling method, and then the resist was peeled off using a resistpeeling solution (1112A, produced by Shipley Company) to form anobjective pattern and a platinum electrode having a distance betweenelectrodes of 20 μm, a width of 60 μm and a length of 120 μn.

Example 9-1

[0128] A platinum electrode was formed in the same manner as in Example9 except for changing the metal organic compound solution to a Pt—Bisolution (platinum (II) monoethanolamine acetate complex.platinumcontent: 2% by weight/EDTANH4-bismuth (III) acetate.bismuth content: 200ppm) and changing the dipping time to 90 seconds.

[0129] A platinum electrode having a distance between electrodes of 20μm, a width of 60 μm, a length of 120 μm and a thickness of 32 nm wasformed. The sheet resistance of this electrode was 66 Ω/□.

Example 9-2

[0130] A platinum electrode was formed in the same manner as in Example9 except for changing the metal organic compound solution to a Pt—Sisolution (platinum (II) monoethanolamine acetate complex platinumcontent: 2% by weight/3-(2-aminoethyl)propyltriethoxysilane.siliconcontent: 200 ppm) and changing the dipping time to 60 seconds.

[0131] A platinum electrode having a distance between electrodes of 20μm, a width of 60 μm, a length of 120 μm and a thickness of 78 nm wasformed. The sheet resistance of this electrode was 105 Ω/□.

Example 10

[0132] A resin (polyvinyl alcohol) was coated over the entire surface ofa glass substrate (75 mm in length×75 mm in width×2.8 mm in thickness)with a spin coater and dried at 45° C. for 2 minutes using a hot plate.Subsequently, the entire surface of the substrate was exposed for 2seconds in exposing time by an ultra-high pressure mercury lamp(illuminance: 8.0 mW/cm²) as a light source. Thereafter, the resultingsubstrate was processed by dipping for 30 seconds in pure water as adeveloper. The film thickness thereof was 2.3 μm.

[0133] This substrate was dipped in pure water for 30 seconds and then,dipped in a Pt solution (platinum (II) monoethanolamine acetatecomplex.platinum content: 2% by weight) for 120 seconds.

[0134] Subsequently, the substrate was taken out from the Pt solution,washed with a flowing water for 5 seconds to wash the Pt complexsolution between the resin patterns, dewatered with air and dried for 3minutes by a hot plate at 80° C.

[0135] Thereafter, the substrate dried was burned at 500° C. for 30minutes in a circulating hot air oven to form a platinum electrodehaving a distance between electrodes of 20 μm. a width of 60 μm, alength of 120 μm and a thickness of 40 nm.

[0136] The sheet resistance of this electrode was 18 Ω/□.

[0137] Subsequently, a resist (positive-type resist LC100/10 cp,produced by Shipley Company) was coated (1200 rpm/5 seconds, filmthickness: 1.3 micron) on this substrate with a spinner.

[0138] The coated resist was etched (etching conditions are:acceleration voltage: 500 V, current: 600 mA, deceleration voltage: 200V, gas seed: argon 255 CCM and carrier speed: 5 mm/second) by ionmilling method, and then the resist was peeled off using a resistpeeling solution (1112A, produced by Shipley Company) to form anobjective pattern and a platinum electrode having a distance betweenelectrodes of 20 μm, a width of 60 μm and a length of 120 μm.

Example 11

[0139] A metal organic compound aqueous solutiontetrakis(monoethanolamino)platinum (II) acetate complex platinumcontent: 5% by weight and a resin (polyvinyl alcohol) aqueous solutionwere mixed in the following ratio to thereby prepare a composition 11-A.

[0140] Metal organic compound: 50 parts by weight

[0141] Polyvinyl alcohol resin: 50 parts by weight

[0142] This composition 11-A was coated over the entire surface of aglass-made substrate (75 mm in length×75 mm in width×2.8 mm inthickness) with a spin coater and dried at 80° C. for 2 minutes. Thefilm thickness after drying was 2.1 μm.

[0143] Subsequently, the substrate having coated film was placed in acirculating hot air oven and burned at 500° C. for 30 minutes. As aresult, a platinum having a thickness of 60 nm was formed. Using asimultaneously-formed platinum film pattern having a size of 1 cm×1 cm,the sheet resistance was measured, and it was found to be 14 Ω/□.

[0144] Thereafter, on this substrate, a resist (positive-type resistLC100/10 cp, produced by Shipley Company) was coated (1200 rpm/5seconds, film thickness: 1.3 micron) with a spinner.

[0145] The coated resist was etched (etching conditions are:acceleration voltage: 500 V, current: 600 mA, deceleration voltage: 200V, gas seed: argon 255 CCM and carrier speed: 5 mm/second) by an ionmilling method, and then the resist was peeled off using a resistpeeling solution (1112A, produced by Shipley Company) to form anobjective pattern and a platinum electrode having a distance betweenelectrodes of 20 μm, a width of 60 μm and a length of 120 μm.

Example 12

[0146] A solution obtained by adding 0.06 wt % of an amine silanecoupling agent (KBM-603, produced by Shin-Etsu Chemical Co., Ltd.) to aphotosensitive resin (sun resiner BMR-850, produced by Sanyo Kasei Co.,Ltd.) was coated over the entire surface of a glass substrate (75 mm inlength×75 mm in width×2.8 mm in thickness) with a spin coater and driedat 45° C. for 2 minutes using a hot plate. Subsequently, the substrateand the mask were brought into contact with each other, and the entiresurface of the substrate was exposed for 2 seconds in exposing time byan ultra-high pressure mercury lamp (illuminance: 8.0 mW/cm²) as a lightsource. Thereafter, the resulting substrate was processed by dipping for30 seconds in pure water as a developer, thus obtaining an objectivepattern. The film thickness thereof after the pattern formation was 1.55μm.

[0147] This substrate was dipped in a Pt complex solution (platinum (II)monoethanolamine acetate complex.platinum content: 2% by weight) for 120seconds.

[0148] Subsequently, the substrate was taken out from the Pt complexsolution, washed with flowing water for 5 seconds to wash the Pt complexsolution between the patterns, dewatered with air and dried for 3minutes by a hot plate at 80° C.

[0149] Thereafter, the substrate dried was burned at 500° C. for 30minutes in a circulating hot air oven to form a platinum electrodehaving a thickness of 76 nm.

[0150] The sheet resistance of this electrode was 9 Ω/□.

[0151] Thereafter, on this substrate, a resist (positive-type resistLC100/10 cp, produced by Shipley Company) was coated (1200 rpm/5seconds, film thickness: 1.3 micron) with a spinner.

[0152] The coated resist was etched (etching conditions are:acceleration voltage: 500 V, current: 600 mA, deceleration voltage: 200V, gas seed: argon 255 CCM and carrier speed: 5 mm/second) by an ionmilling method, and then the resist was peeled off using a resistpeeling solution (1112A, produced by Shipley Company) to form anobjective pattern and a platinum electrode having a distance betweenelectrodes of 20 μm, a width of 60 μm and a length of 120 μm.

Example 13

[0153] A metal organic compound bis(acetylacetonato)platinum (II) and anacrylic copolymer resin propylene glycol monomethyl ether solution weremixed in the following ratio to prepare a composition 13-A.

[0154] Metal organic compound: 50 parts by weight

[0155] Acrylic copolymer resin: 50 parts by weight

[0156] This composition 13-A was coated over the entire surface of aglass-made substrate (75 mm in length×75 mm in width×2.8 mm inthickness) with a spin coater and dried at 80° C. for 2 minutes by a hotplate. The film thickness thereof after drying was 1.5 μm.

[0157] Subsequently, the substrate having the coated film was placed ina circulating hot air oven and burned at 550° C. for one hour. As aresult, a platinum having a thickness of 42 nm was formed. The sheetresistance of this platinum was measured, and it was found to be 35 Ω/□.

[0158] Thereafter, on this substrate, a resist (positive-type resistLC100/10 cp, produced by Shipley Company) was coated (1200 rpm/5seconds, film thickness: 1.3 micron) with a spinner.

[0159] The coated resin was etched (etching conditions are: accelerationvoltage: 500 V, current: 600 mA, deceleration voltage: 200 V, gas seed:argon 255 CCM and carrier speed: 5 mm/second) by an ion milling method,and then the resist was peeled off using a resist peeling solution(1112A, produced by Shipley Company) to form an objective pattern and aplatinum electrode having a distance between electrodes of 20 μm, awidth of 60 μm and a length of 120 μm.

Example 14

[0160] A cyclized rubber and a 4,4′-diazidochalcone xylene solution weremixed in the following ratio to prepare a composition 14-A.

[0161] Cyclized rubber: 95 parts by weight

[0162] 4,4′-diazidochalcone: 5 parts by weight

[0163] This composition 14-A was coated over the entire surface of aglass-made substrate (75 mm in length×75 mm in width×2.8 mm inthickness) with a spin coater and dried at 80° C. for 2 minutes using ahot plate. The film thickness thereof after drying was 1.5 μm.

[0164] Subsequently, using a negative photomask, the substrate and themask were brought into contact with each other, and an exposure wasperformed thereon for 10 seconds in exposing time by an ultra-highpressure mercury lamp (illuminance: 8.0 mW/cm²) as a light source.Thereafter, the resulting substrate was processed by dipping for 30seconds in xylene as a developer to obtain an objective resin pattern.The film thickness thereof after the pattern formation was 1.0 μm.

[0165] This substrate was dipped in a Pt complex acetone solution(bis(acetylacetonato)platinum (II) platinum content: 2% by weight) for30 seconds.

[0166] Subsequently, the substrate was taken out from the Pt complexacetone solution, washed with flowing water for 5 seconds to wash the Ptcomplex solution between the patterns, dewatered with air and dried for3 minutes by a hot plate at 80° C.

[0167] Thereafter, the substrate dried was burned at 500° C. for 30minutes in a circulating hot air oven to form a platinum electrodehaving a thickness of 25 nm.

[0168] The sheet resistance of this electrode was 100 Ω/□.

Comparative Example

[0169] On a glass-made substrate (75 mm in length×75 mm in width×2.8 mmin thickness), Ti was first deposited at a thickness of 5 nm and Pt wassubsequently deposited at a thickness of 45 nm by sputtering method.Subsequently, on this substrate, a resist (positive-type resist LC100/10cp, produced by Shipley Company was coated (1200 rpm/5 seconds, filmthickness: 1.3 pm) with a spinner.

[0170] The coated film was etched (etching conditions are: accelerationvoltage: 500 V, current: 600 mA, deceleration voltage: 200 V, gas seed:argon 255 CCM and carrier speed: 5 mm/second) by an ion milling method,and then the resist was peeled off using a resist peeling solution(1112A, produced by Shipley Company) to obtain an objective pattern.Using a simultaneously-formed platinum film pattern having a size of 1cm×1 cm, the sheet resistance was measured, and it was found to be 5.5Ω/□.

[0171] Using EPMA (electron probe•microanalyzer), the substratemanufactured above was subjected to measurement of the Pt amount on thesubstrate.

[0172] The results thereof are shown in Table 1. TABLE 1 Sheet Filmresistance thickness No. (Ω/□) (nm) EPMA Porosity Density Remark DensityComparative 5.5 45 2500 0.00 1.00 Litho ref example  1 60 20 500 0.550.45 Pt-Pb Dense  2 40 25 580 0.58 0.42 Pt Dense  3 55 30 770 0.54 0.46Pt-Pb Dense  6 80 30 400 0.76 0.24 Pt Non-dense  7 120 40 700 0.69 0.32Pt-Pb Non-dense  7-2 12 42 820 0.65 0.35 Pt-Ru Non-dense  7-3 80 56 6500.79 0.21 Pt-Sn Non-dense  7-4 64 38 700 0.67 0.33 Pt-V Non-dense  8 16060 800 0.76 0.24 Pt-Pb Non-dense  8-2 250 44 420 0.83 0.17 Pt-ZnNon-dense  8-3 190 51 800 0.72 0.28 Pt-Rh Non-dense  8-4 99 43 750 0.690.31 Pt-Cr Non-dense  9 39 60 2000 0.40 0.60 Pt-Pb Dense  9-2 66 32 14500.18 0.82 Pt-Bi Dense  9-3 108 78 3500 0.19 0.81 Pt-Si Dense 10 20 401500 0.33 0.68 Pt Dense 11 14 60 2600 0.22 0.78 Pt Dense 12 9 76 29000.31 0.69 Pt Dense 13 35 42 1250 0.46 0.54 Pt Dense 14 100 25 350 0.750.25 Pt Non-dense

[0173] Further, masking was performed on a part of the electrodes of thesubstrate manufactured in Comparative Example and the above-describedsome Examples, and Ag was deposited thereon at a thickness of 500 nm bysputtering.

[0174] This substrate was burned at 400° C. for 1 hour in a circulatinghot air oven.

[0175] Using EPMA, this substrate was measured on the Ag value at aposition of 500 μm from the edge portion generated by sputtering Ag onthe Pt electrode.

[0176] The results thereof are shown in Table 2. TABLE 2 Judgment Resis-manufac- Por- of tance turing Overall No. osity Ag Diffusion StabilityCost Judgement Comparative 0 1000 X ◯ X X example Example 1 0.55 200 ◯ ◯◯ ⊚ Example 2 0.58 180 ◯ ◯ ◯ ⊚ Example 6 0.76 110 ◯ X ◯ Δ Example 7 0.69140 ◯ X ◯ Δ Example 8 0.76 140 ◯ X ◯ Δ Example 9 0.40 250 ◯ ◯ ◯ ⊚Example 9-2 0.18 490 Δ ◯ ◯ ◯ Example 10 0.33 320 ◯ ◯ ◯ ⊚ Example 11 0.22400 ◯ ◯ ◯ ⊚ Example 13 0.46 240 ◯ ◯ ◯ ⊚

Example 15

[0177] Using the same method as in Example 4, a plurality of surfaceconductive-type electron emitting devices were manufactured and, at thesame time, a wiring for driving this plurality of surfaceconductive-type electron-emitting devices was formed to therebymanufacture an electron source and moreover, an image-forming apparatuswas manufactured using this electron source. Here, a pair of deviceelectrodes was prepared so as to have a shape that the distance from thecontact portion of the device electrodes with the wiring to anelectron-emitting portion was 500 μm.

[0178] Note that, a pair of device electrodes was manufactured using thefollowing Examples and Comparative Examples of the present invention.Comparative Examples 2 and 3 are examples in which the film thickness ofthe resin pattern and the dipping time of the resin pattern to a metalsolution in Example 9-2 were desirably controlled and a pattern having adifferent porosity is obtained, for comparing the relation between theporosity and the electron emitting properties.

[0179] In this way, a display panel as shown in FIG. 2 was manufactured,and then a drive circuit comprising a scan circuit, a control circuit, amodulation circuit, a d.c. voltage source and the like (all are notshown) was connected thereto to manufacture a panel-form image-formingapparatus.

[0180] A predetermined voltage was applied by time sharing to eachsurface conductive-type electron emitting device through the X-directionterminals D_(X1) to D_(Xn) and the Y-direction terminals D_(Y1) toD_(Ym), and a high voltage was applied to the metal back 9 through thehigh voltage terminal 12, whereby an image pattern was displayed.

[0181] The results thereof were shown in Table 3. TABLE 3 Comparison ofElectron-Emitting No. Porosity Ag Properties Comparative 0 1000 0.5example Comparative 0.08 800 0.76 example 2 Comparative 0.1 750 0.83example 3 Example 1 0.55 200 1 Example 2 0.58 180 0.98 Example 6 0.76110 0.99 Example 7 0.69 140 1 Example 8 0.76 140 1 Example 9 0.40 2500.98 Example 9-2 0.18 490 0.87 Example 10 0.33 320 0.98 Example 11 0.22400 0.93 Example 13 0.46 240 1

[0182] As described above, in order to obtain a preferable electronemitting property in the relation between the electron emittingproperties and the porosity, it can be said that the porosity ispreferably 10% or more, more preferably 20% or more. Taking account ofthe above-described stability of the resistance, it is preferable tosatisfy the porosity of 60% or less. Also, as an electrode pattern, itcan be said that, in view of Ag diffusion, the porosity is preferably10% or more, more preferably 20% or more, and in view of the resistancestability, the porosity is preferably 60% or less.

Example 16

[0183] In this Example and Example 17, a resin pattern was formed usinga resin having an ion exchange function. More specifically, a resinhaving a carboxylic acid group was used. As a result, the absorption ofmetal materials was more improved, and a manufacturing method at a lowcost in which the use efficiency of materials is enhanced can beprovided. Example 16 will be described in detail below. In this Example,a photosensitive resin containing polymer components (methacrylicacid-methylmethacrylicacid-ethylacrylate-n-butylacrylate-azobisisobutyronitrile copolymer) asdescribed in Patent Registration NO. 02527271 was coated over the entiresurface of a glass substrate (75 mm in length×75 mm in width×2.8 mm inthickness) with a roll coater and dried at 45° C. for 2 minutes using ahot plate. Subsequently, using a negative photomask, the substrate andthe mask were contacted with each other, and an exposure was performedthereon for 2 seconds in exposing time by an extra-high pressure mercurylamp (illuminance: 8.0 mW/cm²) as a light source. Thereafter, theresulting substrate was processed by dipping for 30 seconds in purewater as a developing solution to obtain an objective resin pattern. Thefilm thickness of the resin pattern obtained was 1.35 am.

[0184] This resin pattern-formed substrate was dipped in pure water for30 seconds and then dipped in a Pt—Pb solution (platinum (II)monoethanolamine acetate complex:platinum content: 2% by weight/lead(II) acetate:lead content: 200 ppm)) for 60 seconds.

[0185] Subsequently, the substrate was taken out from the Pt—Pbsolution, washed with a flowing water for 5 seconds to wash the Ptcomplex solution between the resin patterns, dewatered by sprayingthereon air and dried for 3 minutes by a hot plate at 80° C.

[0186] Thereafter, the substrate dried was burned at 500° C. for 30minutes in a circulating hot air oven to form a platinum electrodehaving a distance between electrodes of 20 μm, a width of 60 μm, alength of 120 μm and a thickness of 15 nm.

[0187] The sheet resistance of this electrode was 80 Ω/□.

Example 17

[0188] Using the resin pattern manufactured in Example 16, instead ofdipping it in the Pt—Pb solution, the solution was imparted two times onthe resin pattern by an ink jet apparatus (Bubble Jet Printer HeadBC-01, manufactured by Canon Co., Inc.) and dried for 3 minutes by a hotplate at 80° C.

[0189] Thereafter, the substrate dried was burned at 500° C. for 30minutes in a circulating hot air oven to form a platinum electrodehaving a distance between electrodes of 20 μm, a width of 60 μm, alength of 120 μm and a thickness of 15 nm. In case of this Example, thewashing step is not required, and therefore the number of steps can bereduced.

[0190] Also, the sheet resistance of this electrode was 85 Ω/□.

[0191] In Examples 16 and 17 above, also, a pattern was able to beformed with a good use efficiency of materials. Further, the electrodepatterns manufactured according to the methods of Examples 16 and 17above are used for the device electrode of the image-forming apparatusin Example 4. As a result, preferable electron emitting properties wasable to be obtained and a preferable image display was able to berealized.

[0192] The present invention is as described above, and exhibits thefollowing effects.

[0193] (1) The materials constituting a pattern are scarcely removed inthe course of the process for forming the metal or the metal compoundpattern, and therefore, for example, at the formation of an electricallyconductive pattern such as an electrode or a wiring, electricallyconductive pattern constituting materials that are to be removed duringthe process can be suppressed to the minimum, and even when theelectrically conductive pattern is constituted by a noble metal such asplatinum, a load bearing at the time of recovering and reusing theelectrically conductive pattern constituting materials that are to beremoved during the process can be reduced to the minimum. Further, if anelectron emitting device, an electron source and an image-formingapparatus are manufactured using this method of forming the electricallyconductive pattern, the above-described load at the time ofmanufacturing those can be greatly reduced.

[0194] (2) From the same reason as that described above, since a patterncan be formed using the minimum required amount of metal component, thecost required at the time of forming a large number of electrodes,wiring patterns or insulating layers over a large area can besuppressed.

[0195] (3) In the present invention, a water-soluble photosensitiveresin is used as a photosensitive resin and a solution containing metalcomponents is prepared as an aqueous solution, whereby an adverseinfluence exerted on the natural environment in addition to a workingenvironment can be suppressed to the minimum and, at the same time, apatterning does not require the use of a strong acid, with the resultthat there is no fear that the precision decreases due to the corrosionof the substrate due to a strong acid, and a desired fine electricallyconductive pattern can be formed without lowering the precision.

[0196] (4) In particular, by selecting such a metal organic compound (ametal complex having a specified ligand) that a crystal is hardlyprecipitated in the drying step, a metal film formed as an electricallyconductive pattern can be rendered an uniform with good quality.

[0197] Further, an embodiment mode in which the porosity is controlledexhibits the following effects.

[0198] (5) If a film quality of a metal or a metal compound pattern iscontrolled, the use ratio of materials is reduced while maintaining theelectrical properties as a pattern, such as the resistance in the caseof using it as an electrode or the insulating property in the case ofusing it as an insulating layer, as a result, whereby the cost can bereduced.

[0199] (6) The diffusion and movement of the dissimilar metal can begreatly suppressed in the presence of dissimilar metal.

[0200] (7) In particular, when the pattern is used for an electrodeconstituting an electron emitting device, the deterioration of electronemitting properties due to diffusion of dissimilar metals can beprevented and a preferable image-forming apparatus can be provided.

What is claimed is:
 1. A method of manufacturing a metal or metalcompound pattern, comprising: a resin pattern forming step of forming onthe surface of a substrate a resin pattern capable of absorbing asolution containing metal components; an absorbing step of dipping saidresin pattern in said solution containing metal components to make saidresin pattern absorb said solution containing metal components; awashing step of washing the substrate having formed thereon the resinpattern that has absorbed said solution containing metal components; anda burning step of burning said resin pattern after washing.
 2. A methodof manufacturing a metal or metal compound pattern, comprising: a resinpattern forming step of forming on the surface of a substrate a resinpattern capable of absorbing a solution containing metal components; anabsorbing step of coating said solution containing metal components ontosaid resin pattern by a spray method or a spin coat method to make saidresin pattern absorb said solution containing metal components; awashing step of washing the substrate having formed thereon the resinpattern that has absorbed said solution containing metal components; anda burning step of burning said resin pattern after washing.
 3. Themethod of manufacturing a metal or metal compound pattern according toclaim 1 or 2, wherein said resin is a photosensitive resin.
 4. Themethod of manufacturing a metal or metal compound pattern according toclaim 1 or 2, wherein said solution containing metal components is anaqueous solution obtained by dissolving a water-soluble metal organiccompound in an aqueous solvent component.
 5. The method of manufacturinga metal or metal compound pattern according to claim 4, wherein saidmetal components are mainly a platinum complex.
 6. The method ofmanufacturing a metal or metal compound pattern as claimed in claim 1 or2, wherein as said metal components, at least any one of elemental formsof rhodium, bismuth, ruthenium, vanadium, chromium, tin, lead andsilicon or the compound thereof is contained.
 7. The method ofmanufacturing a metal or metal compound pattern according to claim 3,wherein the resin pattern forming step comprises: a coating step ofcoating said photosensitive resin on a substrate; an exposing step ofexposing said photosensitive resin film to obtain a predeterminedpattern; and a developing step of developing said photosensitive resinfilm that has been exposed to thereby form a resin pattern.
 8. A patterncomprising: a first region having one of a first metal and a first metalcompound and having a porosity of 60% or less; and a second regiondisposed so as to be in contact with said first region and having one ofa second metal and a second metal compound which is different from theone of said first metal and said first metal compound.
 9. The patternaccording to claim 8, wherein said porosity is 10% or more.
 10. Thepattern according to claim 8, wherein the porosity is 20% or more. 11.The pattern according to claim 8, wherein said pattern haselectroconductivity.
 12. The pattern according to claim 8, wherein saidfirst region and/or said second region is an electrode.
 13. The patternas claimed in claim 8, wherein said first region and/or said secondregion is a wiring.
 14. A method of manufacturing a metal or metalcompound, comprising: a resin pattern forming step of forming on thesurface of a substrate a resin pattern capable of absorbing a solutioncontaining metal components and capable of ion-exchanging said metalcomponents; an absorbing step of making said resin pattern absorb saidsolution containing metal components; and a burning step of burning theresin pattern that has absorbed said solution containing metalcomponents.
 15. The method of manufacturing a metal or metal compoundpattern according to claim 14, wherein said ion-exchangeable resin has acarboxylic acid group.